CN1238769A - Sugar compounds, gelling agents, gelling agent compositions, processes for the preparation of them and gel compositions - Google Patents

Sugar compounds, gelling agents, gelling agent compositions, processes for the preparation of them and gel compositions Download PDF

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CN1238769A
CN1238769A CN97180039A CN97180039A CN1238769A CN 1238769 A CN1238769 A CN 1238769A CN 97180039 A CN97180039 A CN 97180039A CN 97180039 A CN97180039 A CN 97180039A CN 1238769 A CN1238769 A CN 1238769A
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sugar compounds
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CN1101389C (en
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小林稔明
安藤健司
野本春朝
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New Japan Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/042—Gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/902—Gelled emulsion

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Abstract

Gelling agents containing at least one of the sugar compounds represented by general formulae (1) and (2) wherein R<1> and R<2> are each independently C1-C3 alkyl, C1-C3 alkoxyl or halogeno; and p is 0 or 1. The gelling agents are extremely useful for aqueous media.

Description

Sugar compounds, jelling agent, latex agent composition prepares their method and gelatinous composition
Invention field
The present invention relates to new useful sugar compounds, this sugar compounds the preparation method, contain the organic gelling agent of described sugar compounds, the heating reversible gel made from described organic gelling agent, the preparation method and its usage of this gel.
The invention still further relates to new useful latex agent composition, this composition can be used for water medium, the present invention also relates to the preparation method of this latex agent composition, and with the gelatinous composition of this latex agent composition preparation.
From the angle of industrial significance, term used herein " gel " or refer to a kind of state of matter, wherein said material is not flowable, and although it contains a large amount of media, its yield value is at least 60g/cm 2, perhaps refer to be in the material of this state.In addition, term used herein " latex agent composition " refers to can make medium agglomerative composition when being dissolved in or be scattered in medium.Term used herein " gelatinous composition " refers to contain the gel of at least a latex agent composition and a kind of medium as moiety.
Background of invention
Even use dibenzylidene sorbitol derivative or dibenzylidene xyllitol derivative also can make many organic solvents or polymkeric substance generation gelling (people such as Kobayashi on a small quantity, " Japanese rheology meeting magazine (Journal of Japan Rheology Society) ", the 17th volume, people such as the 104th page (1989) and Kobayashi, " Japanese rheology meeting magazine (Journal of Japan RheologySociety) ", the 17th volume, the 112nd page (1989).These derivatives are used in during many kinds use, mainly as solid marking agent, solid binder, waste oil jelling agent, be used for polyolefinic sol-gel transition type and examine agent etc. clearly.But said derivative only is dissolved in water a little, therefore can not be alone as the jelling agent of water.
It is known being used for forming the multiple high molecular jelling agent that heats the reversible aqueous gel, and comprise non-electrolytic polymerization thing such as natural polymer amount starch or derivatived cellulose, electrolytic polymerization thing such as alginic acid, agar and carrageenin, and contain protein polymer such as gelatin, collagen and casein.In paper nappy was made, the multipolymer of synthetic polymkeric substance such as polyvinyl alcohol and sodium polyacrylate, semi synthetic polymer such as starch-vinylformic acid transplanting polymkeric substance etc. was widely used as water absorbent polymer.But natural materials has the shortcoming of decomposition.The gel formation ability of electrolytic polymerization thing is subjected to having a strong impact on of salt, and it obviously suffers damage when having salt to exist.Because the dissolution rate of these polymkeric substance in water is very low and what obtain is the colloidal sol system of high viscosity, so just the operation efficiency problem occurred.
Sericin is a kind of amino acid material of specific type of costliness, and it has the water of making agglomerative ability, but its gelling ability obviously is subjected to tart influence in the system.And sericin also has problems aspect preservation.Owing to these reasons, sericin does not also obtain practical application.
When coming the gelation water medium, to be used in combination organic solvent with conventional lower molecular weight jelling agent (being generally the dibenzylidene sorbitol derivative) basically.
In sum, what people pressed for most is not have said shortcoming, not resolvent neutral lower molecular weight organic gelling agent when promptly storing, and they can not bring negative impact to environment, and show high-level efficiency in the gelatigenous process of colloidal sol that by dissolving the time, forms, and the influence that not existed by inorganic salt.
Disclosure of the Invention
One of the object of the invention provides new useful lower molecular weight organic gelling agent, and it can be used to the gelation water medium.
Even another purpose of the present invention provides in the environment that can not use thermal source also the latex agent composition of gelation water medium at an easy rate.
According to above-mentioned viewpoint, the inventor has carried out extensive studies to the water medium gelling of multiple low molecular weight organic compound, the sugar compounds that discovery has a special construction that did not disclose in the document has makes the remarkable ability of water medium agglomerative specially, and find, the organic gelling agent that contains this sugar compounds is neutral lower molecular weight organic gelling agent, it not only has the gelling ability of the inorganic salt influence that exists in the system of not being subject to, and also can not decompose when storing.It can not have a negative impact to environment, and can be issued to the gelatigenous purpose of high-level efficiency in the situation that sol phase need not be tackified.The present invention just is based on that these new discoveries finish.
The feature of sugar compounds of the present invention is represented by formula (1) or formula (2):
Figure A9718003900091
Wherein, R 1And R 2Identical or different, representative has the alkyl of 1-3 carbon atom, the alkoxyl group that 1-3 carbon atom arranged or halogen atom separately, and p is 0 or 1.
The inventor has carried out extensive studies to the water medium gelling of multiple low molecular weight organic compound, discovery is (heating simultaneously when the composition dissolves of the special formulation of sugar compounds that contains special construction and dispersion agent is in water medium, cooling then), gel can be formed, and under situation about not heating, also gel can be formed at an easy rate near room temperature.The present invention is accomplished based on this new discovery.
Latex agent composition of the present invention contains at least a sugar compounds in the sugar compounds that 100 weight parts are selected from the sugar compounds of formula (1) expression and formula (2) expression, be selected from least a dispersion agent of following material with the 1-1000 weight part: nonionogenic tenside, anion surfactant, cats product, amphoterics and hydrophilic organic solvent
Figure A9718003900101
Figure A9718003900102
Wherein, R 1And R 2Identical or different, representative has the alkyl of 1-3 carbon atom, the alkoxyl group that 1-3 carbon atom arranged or halogen atom separately, and p is 0 or 1.
The example of formula (1) or formula (2) sugar compounds has: single (3-chloro-4-methyl benzylidene)-D-Sorbitol Powder, single (3, the 4-dimethoxybenzylidenegroup group)-the D-Sorbitol Powder, single (3-ethyl-4-methyl benzylidene)-D-Sorbitol Powder, single (3-methyl-4-ethyl benzylidene)-D-Sorbitol Powder, single (3-propyl group-4-methyl benzylidene)-D-Sorbitol Powder, single (3,4-diethyl benzylidene)-and the D-Sorbitol Powder, single (3, the 4-dichlorin benzylidene)-D-Sorbitol Powder, single (3, the 4-dimethyl benzylidene)-and the D-Sorbitol Powder, single (3,4-dipropyl benzylidene)-D-Sorbitol Powder, single (3,4-diethoxy benzylidene)-and the D-Sorbitol Powder, single (3,4-diisopropoxy benzylidene)-sorbitol derivatives such as D-Sorbitol Powder; And single (3-ethyl-4-methyl benzylidene)-Xylitol, single (3-methyl-4-ethyl benzylidene)-Xylitol, single (3-propyl group-4-methyl benzylidene)-Xylitol, single (3,4-diethyl benzylidene)-Xylitol, single (3, the 4-dichlorin benzylidene)-Xylitol, single (3, the 4-dimethyl benzylidene)-Xylitol, single (3,4-dipropyl benzylidene)-Xylitol, single (3-chloro-4-methyl benzylidene)-Xylitol, single (3, the 4-dimethoxybenzylidenegroup group)-Xylitol derivatives such as D-Xylitol.
Sugar compounds of the present invention can prepare with following method.
The method for preparing desired sugar compounds may further comprise the steps: the dehydrating condensation in water or organic solvent with sugar alcohol (A) and benzaldehyde derivative (B), wherein sugar alcohol (A) is one of Sorbitol Powder or Xylitol at least, and benzaldehyde derivative (B) is to be selected from 3 of formula (3) expression, 3 of dibasic phenyl aldehyde of 4-and formula (4) expression, at least a in the dialkyl ether of the dibasic phenyl aldehyde of 4-, sugar alcohol (A) is 2/1 to 1/2 with the mol ratio (A/B) of benzaldehyde derivative (B), thereby generates desired sugar compounds with hyperergy and highly selective.
Figure A9718003900112
Wherein, R 1And R 2Identical or different, representative has the alkyl of 1-3 carbon atom, the alkoxyl group that 1-3 carbon atom arranged or halogen atom, R separately 3Representative has the alkyl of 1-4 carbon atom.
Sugar alcohol (A) preferably is that the aqueous solution form of 5-95wt% is used with concentration, more preferably is that the aqueous solution form of 50-80wt% is used with concentration.
The example of benzaldehyde derivative (B) has: 3-chloro-4-tolyl aldehyde, 3,4-dimethoxy benzaldehyde, 3-ethyl-4-tolyl aldehyde, 3-methyl-4-ethylbenzene formaldehyde, 3-propyl group-4-tolyl aldehyde, 3,4-diethylbenzaldehyde, 3,4-dichlorobenzaldehyde, 3,4-dimethylbenzaldehyde, 3,4-dipropyl phenyl aldehyde, 3, the 4-di ethoxy-benzaldehyde, 3,4-diisopropoxy phenyl aldehyde, its dme, its ether, its dipropyl ether and dibutyl ether thereof.Wherein preferred 3,4-dimethylbenzaldehyde and 3,4-dichlorobenzaldehyde.
The mol ratio of used reactive material (A/B) is 2/1 to 1/2.The concentration of reactive material is preferably 5-90wt%, more preferably 15-80wt%.
The dispersion medium that is used to react can be water or organic solvent such as hexanaphthene, methylcyclohexane, dimethylbenzene, toluene etc.Say that from output, economic dispatch angle water is more suitable.Available Sorbitol Powder or xylitol powder are made reactant in using water as the reaction system of dispersion medium.
Reaction is preferably carried out in the presence of an acidic catalyst.Used an acidic catalyst can be any strong acid catalyst.Preferred strong acid catalyst has: sulfuric acid, hydrochloric acid, adjacent-,-or right-toluenesulphonic acids, alkyl (2-18 carbon atom) Phenylsulfonic acid, phosphoric acid and Zeo-karb.
Catalyst consumption is not particularly limited, but its amount is preferably in the 0.05-20wt% scope of reactant (composition (A)+(B)) gross weight, more preferably in the scope of 1-10wt%.
Preferred 80 ℃ or lower of temperature of reaction, more preferably 15-40 ℃.
Need be with to come the air in the surrogate response system as the benzaldehyde derivative inert gasses of raw material such as nitrogen and carbon dioxide.
Reaction times is not had particular restriction, but the reaction times be generally 1-50 hour, be preferably 3-10 hour.
After reaction finishes, when stirring, use alkali neutralization reaction mixture.The mixture that neutralized is filtered, washs and drying.Available alkali has, for example, and sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate and water glass.These alkali can powder, any form is used in particle and the solution.If use the alkali of solution form, then its concentration there is not particular restriction, but preferred 5-10wt%.The solvent of washing usefulness can be water, water with organic solvents such as the solvent mixture of the lower alcohol that 1-3 carbon atom arranged formation or hexane, hexanaphthene, toluene, dimethylbenzene in any.If desired, can also carry out recrystallization.
As above Zhi Bei formula (1) or formula (2) sugar compounds can be used as the very useful jelling agent of gelation water medium.The feature of organic gelling agent of the present invention is to contain at least a said sugar compounds.
Sugar compounds of the present invention comprises: as 1 of the positional isomers of 6 Yuan diox type acetal rings, 3-O-isomer (corresponding to formula (2) compound) and 2,4-O-isomer (corresponding to formula (1) compound).Any and composition thereof in these positional isomerss can be effectively as the jelling agent of gelation water medium.Wherein, from the ability 2 of gelation water medium, 4-O-(3, the dibasic benzylidene of 4-)-D-Sorbitol Powder and 2,4-O-(3, the dibasic benzylidene of 4-)-the D-Xylitol is preferred 2,4-O-isomer, more preferably 2,4-O-(3, the 4-dimethyl benzylidene)-and D-Sorbitol Powder and 2,4-O-(3, the 4-dimethyl benzylidene)-D-Xylitol.
Can prepare gel of the present invention by following steps: organic gelling agent of the present invention is added in the concrete water medium, and heated mixt dissolves jelling agent in medium, then gained solution is cooled off.
Consumption to jelling agent does not have particular restriction.Be generally the 0.02-10wt% of water medium according to the suitable amounts of used gel, preferred 0.4-5wt%.Generally, the hardness along with the increase gel of jelling agent consumption will increase to some extent.If the content of jelling agent is equal to or less than 1.8wt%, be easy to form transparent gelling.
Heating temperature there is not particular restriction, still, under standard atmosphere pressure, preferably 100 ℃ or lower, preferred 50-100 ℃.Boosting (specifically, up to 50kg/cm 2G) under the situation, preferably 200 ℃ or lower, preferred 100-150 ℃.
In forming gelation process, can adopt any type of cooling that is fit to needs, for example, slowly cooling or cooling rapidly.More particularly, if colloidal sol (flowable solution) is cooled off, through obtaining not flowable gel after the sol-gel conversion.Cooling temperature is 10-50 ℃, preferred 20-40 ℃.
Can be comprised by organic gelling agent agglomerative water medium of the present invention, for example, water, the aqueous solution, water miscible liquid and aqueous dispersions.These media comprise any aqueous solution, water miscible liquid and the aqueous dispersions that contains water-soluble polymers and/or inorganic salt, also comprise the water miscible liquid that contains vinyl-vinyl acetate copolymer.Water medium also comprises, for example, and water and water-soluble medium such as lower alcohol ， diox, the mixture of THF etc.The concentration of water-soluble polymers, inorganic salt or vinyl-vinyl acetate copolymer is preferably 0.05-20wt% in the water medium.
If when being dissolved with water-soluble polymers in the water medium, the gel that then obtains has higher hardness.The water-soluble polymers that can effectively improve gel hardness comprises that for example, (molecular-weight average is 10 to hydroxypropylcellulose, 000-500,000), (molecular-weight average is 10 to Natvosol, 000-500,000), polyvinyl alcohol (molecular-weight average is 400-100,000), (molecular-weight average is 400-100 to polymethyl vinyl ether, 000) and polyvinylpyrrolidone (molecular-weight average is 400-100,000).
When being used in combination high molecular jelling agent commonly used such as starch, derivatived cellulose, alginic acid or agar, can improve the hardness of gel.
One of characteristics of jelling agent of the present invention are the stability of gained gel and the negative impact that hardness is not vulnerable to inorganic salt, alkali, urea and tensio-active agent in the water medium thereof.More particularly, as water, if use following any medium can form the gel of basically gel hardness being had no effect at an easy rate: the salt of nitrogenous, phosphorus, potassium is (as nitrocalcite, SODIUMNITRATE, calcium phosphate, ammonium phosphate and potassiumphosphate), urea or its salt etc. is dissolved in or is scattered in wherein water medium; The sodium chloride aqueous solution of 1wt% such as seawater; Or the aqueous solution of tensio-active agent, as the aqueous solution of alkyl sulfuric ester, alkyl ether sulphate, Voranol EP 2001, quaternary ammonium salt, amphoterics etc.This shows that jelling agent of the present invention can be used as the material of water holding sanitary napkins (water-retaining sanitarynapkin), it is the same effective with water absorbent polymer and water binding agent (water-holding) in the civil engineering field.
In the presence of jelling agent of the present invention, the aqueous solution of the water miscible liquid of vinyl-vinyl acetate copolymer, the aqueous solution of polyvinyl alcohol or polyvinylpyrrolidone can form gel at an easy rate.Gel can be made the glue rod, also can be filled into the colloid of making respective shapes in the container.This gel also is used as solid binder or solid binder.
Being used for medical purpose gel such as paste can prepare by the medium that gelling contains endermic medicine such as anti-inflammation analgesic.Useful anti-inflammation analgesic has, for example, and wintergreen oil, glycosal and alkyl salicylate, Whitfield's ointment hydroxyalkyl acrylate, methyl alcohol or camphor etc.The content of these anti-inflammation analgesics in water medium is 0.5-30wt%, preferred 3-15wt%.
The gel that is used for the makeup purpose can contain the water medium that tensio-active agent, wetting agent, UV light absorber etc. are used for the activeconstituents of make-up composition by gel and prepare.Cosmetic gel can be used as hair setting agent, cosmetic clean-out system, face's cleaning compositions, face's cosmetic assistant agent, nail polish paste, nail polish remover, lipstick, reodorant (comprising rod shape product) etc.
Jelling agent of the present invention can be in other field widespread use, for example, snowmaking, cryo-preservative (keeping cryogenic material), substratum, solid seasonings, solid agricultural insecticide, solid fertilizer, the desert become the water holding gel, perfume compound, reodorant, artificial gel feed, condensing agent, gel fire retardant, battery electrolyte gel, gel marking agent, ink, coated composition in greenery patches etc.
The new sugar compounds of the present invention is very useful water medium jelling agent.
Latex agent composition of the present invention contains said sugar compounds of 100 weight parts and 1-1000 weight part dispersion agent.
Dispersion agent can quicken the dispersion of sugar compounds in water medium as the gelling composition, promotes gel formation, improves into glue speed and improves gel-strength.
Being used for dispersion agent of the present invention has, for example, and nonionogenic tenside, anion surfactant, cats product, amphoterics and hydrophilic organic solvent.These dispersion agents both can use separately also can be in conjunction with being used for the present invention.
Nonionogenic tenside as dispersion agent has: poly suboxygen alkyl alkyl oxide, poly suboxygen alkyl alkene ether, poly suboxygen alkyl aryl ethers, poly suboxygen alkyl polyalcohol ether, poly suboxygen alkyl fatty acid ester, fatty acid amide, polyalcohols ester, alkyl polysaccharide, amine oxide etc.
Be used for nonionogenic tenside of the present invention, poly suboxygen alkyl alkyl oxide, poly suboxygen alkyl alkene ether and poly suboxygen alkyl aryl ethers are by promptly pure formula (5) compound that is prepared from alkylene oxide reaction of addition reaction,
R 4-O-(AO) n-H (5) wherein, R 4Be the straight or branched alkyl that 6-20 carbon atom arranged, the alkenyl that 6-20 carbon atom arranged or aryl, A is the alkylidene group that 2-4 carbon atom arranged, and reaching n is the average mol of the oxyalkylene group of interpolation, is 0.1-40.
Specific examples with poly suboxygen alkyl alkyl oxide of straight chained alkyl has: the polyoxyethylene hexyl ether, the polyoxypropylene hexyl ether, polyoxy butylene hexyl ether, the polyoxyethylene heptyl ether, the polyoxypropylene heptyl ether, polyoxy butylene heptyl ether, the polyoxyethylene octyl ether, the polyoxypropylene octyl ether, polyoxy butylene octyl ether, polyoxyethylene ether in the ninth of the ten Heavenly Stems, polyoxypropylene ether in the ninth of the ten Heavenly Stems, polyoxy butylene ether in the ninth of the ten Heavenly Stems, polyoxyethylene ether in the last of the ten Heavenly stems, polyoxypropylene ether in the last of the ten Heavenly stems, polyoxy butylene ether in the last of the ten Heavenly stems, polyoxyethylene 11 ethers, polyoxypropylene 11 ethers, polyoxy butylene 11 ethers, polyoxyethylene ten diether, polyoxypropylene ten diether, polyoxy butylene ten diether, polyoxyethylene 13 ethers, polyoxypropylene 13 ethers, polyoxy butylene 13 ethers, polyoxyethylene ten tetraethers, polyoxypropylene ten tetraethers, polyoxy butylene ten tetraethers, polyoxyethylene ten pentaethers, polyoxypropylene ten pentaethers, polyoxy butylene ten pentaethers, the polyoxyethylene margaron, the polyoxypropylene margaron, polyoxy butylene margaron, polyoxyethylene 17 ethers, polyoxypropylene 17 ethers, polyoxy butylene 17 ethers, polyoxyethylene 18 ethers, polyoxypropylene 18 ethers and polyoxy butylene 18 ethers.
Specific examples with poly suboxygen alkyl alkyl oxide of branched-chain alkyl has: polyoxyethylene-(2-ethylhexyl) ether, polyoxypropylene-(2-ethylhexyl) ether, polyoxy butylene-(2-ethylhexyl) ether, polyoxyethylene iso-octyl ether, polyoxypropylene iso-octyl ether, polyoxy butylene iso-octyl ether, the different heptyl ether of polyoxyethylene, the different heptyl ether of polyoxypropylene, the different heptyl ether of polyoxy butylene, the different nonyl ethers of polyoxyethylene, the different nonyl ethers of polyoxypropylene, the different nonyl ethers of polyoxy butylene, polyoxyethylene isodecyl ether, polyoxypropylene isodecyl ether, polyoxy butylene isodecyl ether, the different undecyl ether of polyoxyethylene, the different undecyl ether of polyoxypropylene, the different undecyl ether of polyoxy butylene, polyoxyethylene Permethyl 99A. base ether, polyoxypropylene Permethyl 99A. base ether, polyoxy butylene Permethyl 99A. base ether, polyoxyethylene isotridecyl ether, polyoxypropylene isotridecyl ether, polyoxy butylene isotridecyl ether, the different myristyl ether of polyoxyethylene, the different myristyl ether of polyoxypropylene, the different myristyl ether of polyoxy butylene, the different pentadecyl ether of polyoxyethylene, the different pentadecyl ether of polyoxypropylene, the different pentadecyl ether of polyoxy butylene, polyoxyethylene isocetyl ether, polyoxypropylene isocetyl ether, polyoxy butylene isocetyl ether, the different heptadecyl ether of polyoxyethylene, the different heptadecyl ether of polyoxypropylene, the different heptadecyl ether of polyoxy butylene, polyoxyethylene isooctadecane base ether, polyoxypropylene isooctadecane base ether, polyoxy butylene isooctadecane base ether, polyoxyethylene-(2-hexyl decyl) ether, polyoxypropylene-(2-hexyl decyl) ether, polyoxy butylene-(2-hexyl decyl) ether, polyoxyethylene-(2-octyl group dodecyl) ether, polyoxypropylene-(2-octyl group dodecyl) ether and polyoxy butylene-(2-octyl group dodecyl) ether.
The specific examples of poly suboxygen alkyl alkene ether has: polyoxyl 10 oleyl ether, polyoxypropylene oil ether and polyoxy butylene oil ether.
The specific examples of poly suboxygen alkyl aryl ethers has: polyoxyethylene to octyl phenyl ether, polyoxypropylene to octyl phenyl ether, polyoxy butylene to octyl phenyl ether, polyoxyethylene to nonylplenyl ether, polyoxypropylene to nonylplenyl ether, polyoxy butylene to nonylplenyl ether, polyoxyethylene to dodecylphenyl ether, polyoxypropylene to dodecylphenyl ether and polyoxy butylene to dodecylphenyl ether.
The mole number that participates in the alkylene oxide of addition reaction is represented with mean value usually.This average mol is the 0.1-40 mole, preferred 2-20 mole.
Preferred its HLB is about those compounds of 5-20 in said poly suboxygen alkyl alkyl oxide and poly suboxygen alkyl alkene ether.The product of the addition reaction of the alkylene oxide that preferably is 2-20 by the saturated or unsaturated alcohol and the average mol of 10-20 carbon atom in this poly suboxygen alkyl alkyl oxide and the poly suboxygen alkyl alkene ether.
The example that is used as the poly suboxygen alkyl polyalcohol ether of dispersion agent is that those are by alkylene oxide such as oxyethane, 1,2-propylene oxide or butylene oxide ring and following material: carbohydrate such as glucose, fructose or sucrose, sugar alcohol such as Sorbitol Powder, Xylitol or maltose alcohol (maltitol), glycol such as ethylene glycol or propylene glycol, the compound that polyalcohols such as glycerine, tetramethylolmethane or trimethylammonium alcohol propane carry out the addition reaction preparation.Wherein, preferably be the compound of the addition reaction preparation that participates in of the alkylene oxide of about 1-50 by average mol.
Comprise that as the example of the poly suboxygen alkyl fatty acid ester of dispersion agent by saturated or unsaturated fatty acids that 8-20 carbon atom arranged and average mol be the compound that the addition reaction between the alkylene oxide that 2-4 carbon atom arranged of 0.1-40 prepares.Wherein preferred compound is to be the alkylene oxide of 2-20 such as the compound that the addition reaction between the polyoxyethylene grease prepares by saturated or unsaturated fatty acids that 8-18 carbon atom arranged and average mol.
The fatty acid amide that can be used as dispersion agent comprises for example, the alkanolamide (alkanol has 1-6 carbon atom) of the saturated or unsaturated fatty acids of 8-20 carbon atom being arranged.The lower alkane alcohol amide (alkanol has 2-4 carbon atom) that the saturated or unsaturated fatty acids of 12-18 carbon atom is preferably arranged.
Other material that can be used as dispersion agent is to be the derivative that the addition reaction between the alkylene oxide of 1-40 is made by said fatty acid amide and average mol.
The example that is used as the polyalcohols ester of dispersion agent is lipid acid and the following material that 2-18 carbon atom arranged: carbohydrate such as glucose, fructose or sucrose, sugar alcohol such as Sorbitol Powder, Xylitol or maltose alcohol, glycol such as ethylene glycol or propylene glycol, the ester that polyalcohols such as glycerine, tetramethylolmethane or trimethylammonium alcohol propane form.Preferably have the polyalcohols ester of the lipid acid of 12-18 carbon atom.
Other material that can be used as dispersion agent is to be the fatty acid ester of the polyalcohols made of the addition reaction between the alkylene oxide of 1-40 by said polyalcohols and average mol.
The APG that can be used as dispersion agent can be used formula (6) expression,
(G) m-O-R 5(6) wherein G is pentose or hexose, and m is this sugared mean polymerisation degree, is 1-10, R 5Be alkyl and the thiazolinyl that 6-20 carbon atom arranged.
The example of APG has: decyl dextran glycosides, dodecyl dextran glycosides, tetradecyl dextran glycosides, the poly-galactoside of decyl, the poly-galactoside of dodecyl, the poly-galactoside of tetradecyl, decyl levan glycosides, dodecyl levan glycosides and tetradecyl levan glycosides.
The mean polymerisation degree of APG is the 1-10 mole, preferred 1-3.0 mole.The HLB of preferred APG is about 10-15.
Other material that can be used as dispersion agent is to be the derivative of the addition reaction preparation between the alkylene oxide of 1-40 by said APG and average mol.
Can use formula (7) expression as the amine oxide of dispersion agent,
R 6-N (R 7) (R 8)-O (7) is R wherein 6Be alkyl and the thiazolinyl that 6-18 carbon atom arranged, R 7And R 8Be respectively methyl or ethyl.
From the angle of dispersing property, in amine oxide, preferably has the amine oxide of 10-12 carbon atom.
The example that is used as the anion surfactant of dispersion agent has: the metal-salt of alkyl or alkenyl vitriol, sulfated alkyl ether, alkyl phenyl ether sulfate, alkylbenzene sulfonate, sulfosuccinate ester salt, lipid acid and alkyl or alkenyl ether carboxylate.
From the angle of dispersing property, wherein preferably have the sulfated alkyl ether of the alkyl or alkenyl vitriol of about 12-20 carbon atom, 12-20 the carbon atom of having an appointment and contain the sodium salt of the lipid acid of alkyl or alkenyl with about 12-20 carbon atom.
The example that is used as the cats product of dispersion agent has: quaternary ammonium salt, particularly tetraalkylammonium salt reach the ammonium salt by the addition reaction preparation of alkylene oxide.
Angle from dispersing property, wherein preferably have a trimethylammonium alkyl ammomium chloride with 12-18 carbon atom alkyl, two dimethyl dialkyl ammonium chlorides with 12-18 carbon atom alkyl are arranged, and have the N of 12-18 carbon atom alkyl, two (polyoxyethylene) alkyl methyl ammonium chlorides of N-.
Example as the zwitterionics of dispersion agent has, for example, and based on amino acid or based on the tensio-active agent of trimethyl-glycine.Wherein preferably the have an appointment alkyl dimethyl Padil trimethyl-glycine of 8-20 carbon atom.
As the hydrophilic organic solvent of dispersion agent is uniform solvent during with required mixed with water.Specific examples has polyalkylene glycol and polyvalent alcohol.
Comprise as the polyalkylene glycol of dispersion agent, for example, polyoxyethylene glycol, polypropylene glycol etc.Preferred polyalkylene glycol is by by about 0.1-150 mole, the compound that the addition reaction of the alkylene oxide of preferably about 1-100 mole is made.
Polyvalent alcohol as dispersion agent has, for example, and carbohydrate such as glucose, fructose and sucrose, sugar alcohol such as Sorbitol Powder, Xylitol and maltose alcohol, glycol such as ethylene glycol and propylene glycol, glycerine, tetramethylolmethane and trimethylammonium alcohol propane.
It can be various forms of being used for dispersion agent of the present invention, as crystal, powder, cream slurry and solution, also can be to make dispersion agent can be at an easy rate mix with medium (especially water medium) in the latex agent composition or make it to be scattered in wherein any form.Described dispersion agent generally should be able to be dissolved in the water medium at an easy rate.Therefore, dispersion agent preferably starch or solution form, the more preferably dispersion agent of solution form by fine crystals, powder, cream.
The consumption that is used for dispersion agent of the present invention depends on the weight ratio with respect at least a sugar compounds, described sugar compounds is selected from formula (1) and formula (2) sugar compounds, make that the consumption with respect to this sugar compounds dispersion agent of 100 weight part weight is a 1-1000 weight part weight, be preferably the 10-500 weight part.If excess is used dispersion agent, the gelling ability in the then non-heating system will reduce.On the other hand, the consumption that reduces dispersion agent will reduce the dispersive ability of sugar compounds, so just is difficult to form homogeneous gel.
For with meticulous solid dispersed in liquid, the concentration of dispersion agent (is for example used to approach micelle-forming concentration (C.M.C.) always, about 500ppm or lower) (" tensio-active agent (Surfactant) ", Kodan Sha Scientific edits, published the 69-82 page or leaf in 1979).But the dispersion agent that is used to disperse sugar compounds in the present invention is using than the concentration of the high order of magnitude of C.M.C., that is, with the high density use of about 5000ppm to about 15wt%, and dispersion agent shows good dispersive ability.
If only make jelling agent and come the gelation water medium without dispersion agent with sugar compounds, then in gelatinization process, need heating or time expand, for example, need 48 hours at least under the room temperature.On the other hand, because latex agent composition of the present invention contains a large amount of dispersion agents (5000ppm at least, more much bigger than conventional amount used), therefore can control gelation time, can make medium gelling immediately or mix back gelling in the time of about 20 minutes with water medium in situation in short-term at latex agent composition, if, be 120 minutes-24 hours in the situation of slack time.
On the other hand, obtain gelatinous composition of the present invention in room temperature and have much higher gel hardness than the gel that obtains without dispersion agent.And These characteristics is producing surprising effect aspect the concentration range of widening the jelling agent that is used for gelatinization process.
This advantage can be supposed from following phenomenon: when jelling agent formed three dimensional network in medium, dispersion agent was thrown on web frame in complicated entanglement mode.More detailed reason remains further to be illustrated.
The hydrophilic organic solvent that is used for one of dispersion agent of the present invention mixes the formation composition with sugar compounds.Like this, the wetting ability of composition has improved, and therefore composition can be dispersed in the water medium better.
Lean on the dispersion agent dispersive and be easy to moistening sugar compounds, make three dimensional network expand whole system to, make whole water medium by gelling because the effect of hydrogen bond makes it with the mode of complexity and near water molecules.
As long as sugar compounds and dispersant just be can be made into latex agent composition of the present invention.
Latex agent composition of the present invention also can be by being suspended in sugar compounds and dispersion agent in a small amount of medium (being substantially equal to the total amount of sugar compounds and dispersion agent), then with suspension at 30-80 ℃, preferred 40-70 ℃ aging 10-300 hour, preferred 24-200 hour, and can prepare by dry according to need products therefrom.
Latex agent composition of the present invention also can make by the following method: with sugar compounds and dispersion agent heating for dissolving in medium such as water, form colloidal sol, again with colloidal sol cool to room temperature to 40 ℃ temperature range, obtain gel, from gel, remove medium under the temperature under low pressure or standard atmosphere pressure in room temperature to 90 ℃ scope.Can be by freezing gel and under the low pressure that is lower than the refrigerant vapour pressure, for example 10 -2Under the low pressure of mmHg, from frozen product, eliminate (freeze-drying) medium, come from gel, to remove medium.
Sugar compounds and dispersion agent suspend or the medium that is dissolved in wherein comprises, for example, the aqueous solution of water medium Ru Shui, salt etc. have the lower alcohol of 1-4 carbon atom such as methyl alcohol, ethanol, propyl alcohol etc. and diox etc.Water medium preferably wherein.
The preferred method of preparation latex agent composition is, for example, the method that may further comprise the steps: at least a dispersion agent that is selected from sugar compounds shown in formula (1) and the formula (2) and 10-500 weight part (preferred 20-400 weight part) with 100 weight parts in the time of heating is dissolved in the water of 5000-20000 weight part, then solution is cooled to 25 ℃ and forms gel, at about-78 ℃ of freezing these gels, decompression removes anhydrate (freeze-drying).
Form as the sugar compounds for preparing latex agent composition starting raw material of the present invention is not had particular restriction, for example, can be particle, powder, fine silt, dry gel powder etc.If only be that sugar compounds and dispersant are made latex agent composition, then preferably use the sugar compounds of dry gel powder form.Term used herein " dry gel powder " refers to by drying or lyophilised gel and removed the powder that medium gets from the gel of being made up of sugar compounds and medium.
Also can not heat latex agent composition of the present invention and prepare gelatinous composition, soon water medium is added in the latex agent composition of the present invention and just can makes gelatinous composition at an easy rate.
In this case, though can near room temperature, easily prepare gelatinous composition usually, also can adopt heating, ultrasonic irradiation or carry out means such as physical agitation to be prepared with agitator etc.
The water medium that is used for preparing gelatinous composition comprises water, the aqueous solution, water miscible liquid and aqueous dispersions.Also can make the mixture of water and at least a non-aqueous media.The example of this non-aqueous media comprises that methyl alcohol, ethanol, propyl alcohol etc. have the lower alcohol of 1-4 carbon atom, dioxan, THF, cellosolve etc.
The consumption of water medium that is used for gelatinous composition is for being the 5-200 weight part with respect to every weight part latex agent composition, preferred 5-150 weight part.If used water medium is less than 5 weight parts, will have the precipitation of jelling agent in the gel that then obtains; If used water medium surpasses 200 weight parts, the gel that then obtains just may be because intensity be low and unstable.
Can contain at least a additive in latex agent composition of the present invention or the gelatinous composition, as antioxidant, stablizer etc., condition is that these additives do not destroy the ability that forms gel.
The example of antioxidant has: oxybenzene compound, phosphite, sulphur compound etc.The consumption of antioxidant is, for example, and the 0.001-3% of latex agent composition weight.
Used stablizer can be divided into two classes: to the stablizer of sugar compounds with to the stablizer of gel structure.
Example to sugar compounds available stablizer has: basic cpd comprises inorganic base salts, as the sodium salt of sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood or ethylenediamine tetraacetic acid (EDTA) (EDTA); The organic acid an alkali metal salt, for example, the sylvite of organic acid such as citric acid, succsinic acid, lactic acid, phenylformic acid or lipid acid or sodium salt; Above-mentioned organic acid alkaline earth salt, for example, said organic acid magnesium salts or calcium salt.The consumption of stablizer is, for example, and the 0.001-3% of latex agent composition weight.
Stablizer to gel structure comprises, for example, and sequestrant such as EDTA.The consumption of this stablizer is, for example, and the 0.001-3% of latex agent composition weight.
Can also contain the additive outside at least a above-mentioned additive in latex agent composition of the present invention or the gelatinous composition, as the tensio-active agent outside inorganic salt, organic salt, seasonings, sanitas (anticeptics), pigment, lower alcohol, the dispersion agent of the present invention, polymkeric substance etc.
Latex agent composition of the present invention or gelatinous composition can be used in combination with other jelling agent commonly used, jelling agent commonly used comprises: lower molecular weight jelling agent such as dibenzylidene sorbitol, hydroxyl-derivative of fatty acid, alkylamide derivatives or cholesterin derivative, or high molecular jelling agent such as agar, gelatin or carrageenin.
One of characteristics of latex agent composition of the present invention are need not heat to form gel at an easy rate.
If prepare gel, then consider that from the deliquescent angle of sugar compounds the concentration of used sugar compounds is about 2wt% at the most with jelling agent (being sugar compounds) with as the water of solvent.Concentration as fructose compound surpasses 1.8wt%, then will produce and contain gel and crystalline mixed system.Yet if prepare gel with latex agent composition of the present invention, jelling agent can use very high concentration, and the gel shape that obtains is stable, and gel hardness is higher.
Because latex agent composition of the present invention can at room temperature form gel at an easy rate, therefore, it can be used for substituting the application of the product of being made by water-absorbing resin, as disposable diaper and health napkin, and be used for hydrogel mat and a kind of pillow used in summer field as product, as the setting accelerator in the water treatment, as the water binding agent in civil engineering field with as the carrier of growing flowers.
Latex agent composition of the present invention can be at an easy rate gelation water medium at room temperature, can in the environment that lacks thermal source, form gel, and can be used for various purposes.
Realize best mode of the present invention
The present invention will be explained in more detail by the following example.
Adopt following method to determine physical properties.Gel hardness is measured
Measure with the instrument (Kiya Seisakusho Ltd. manufacturing) of measuring the agar setting strength.Fusing point is measured
(Yanagimoto Seisaku Sho Co., Ltd. makes) measures 1 ℃/min of temperature rise rate with the instrument of measuring the micro-example fusing point.Measure purity with gas-chromatography (GC)
Undertaken after the pre-treatment by the reaction that changes into trimethyl silyl derivative, carry out gas-chromatography to measure purity with the post of filling siloxanes.Embodiment 1
The 70wt% aqueous solution, the 73.7g (0.55mol) 3 that in a 500mL four neck flasks, pack into and contain 143g (0.55mol) D-Sorbitol Powder, 4-dimethylbenzaldehyde and 12g50wt% sulfuric acid.Go out air in the reaction system with nitrogen replacement.Material in 21 ℃ of stirred flask 6 hours.Analyze the gained reaction mixture with GC, find that the productive rate of single (3, the 4-dimethyl benzylidene)-D-Sorbitol Powder is 70%, productive rate≤0.5% of two (3, the 4-dimethyl benzylidene)-D-Sorbitol Powders.Place and use 8.6g potassium hydroxide neutralization reaction mixture 2 hours after 24 hours, filter and obtain filter cake.Be dispersed in filter cake in the 150mL toluene and filtration once more.Obtain 65g 2 to the 5mmHg pressure range after dry 7 hours at 100 ℃ of normal pressures, 4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder, GC measuring result purity is 99.5% (productive rate 39.7%).The fusing point of product is 199-200 ℃.
Pack in 300mL beaker 99g water and 1g is above-mentioned 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder.With mixture heating up to 96 ℃, stir simultaneously.Obtain the solution (colloidal sol) of homogeneous transparent after 2 minutes.This solution (20mL) is poured in the 300mL sample beaker, and quenching in 20 ℃ of water-baths obtained clear gel after 1 minute.The hardness of measuring gel after 3 hours is 270g/cm 2Gel is heated to 96 ℃ once more, and the gel heating reversibly changes back to homogeneous solution.If, will obtain identical gel once more in the same way as described above with this solution quenching.Embodiment 2
In the 300mL beaker, pack into 99g 1wt% sodium chloride aqueous solution and 1g embodiment 1 gained 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder.Material in the beaker is heated to 96 ℃, stirs simultaneously.Obtain the solution of homogeneous transparent after 2 minutes.This solution (20mL) is poured in the 300mL sample beaker, and quenching in 20 ℃ of water-baths obtained clear gel after 1 minute.The hardness of measuring gel after 3 hours is 280g/cm 2Embodiment 3
Repeat with embodiment 2 same steps, just 1wt% sodium nitrate aqueous solution, 1wt% ammonium phosphate solution and the 1wt% potassiumphosphate aqueous solution with equivalent is total to 99g replacement 1wt% sodium chloride aqueous solution, obtains gel.The hardness of measuring gel after 3 hours is 270g/cm 2Embodiment 4
Repeat with embodiment 1 same step, just replace water, obtain gel with 1wt% polyvinyl alcohol (molecular-weight average (Mn)=700) aqueous solution.The hardness of measuring gel after 3 hours is 470g/cm 2Embodiment 5
Repeat with embodiment 1 same step, just the emulsion with the 25wt% ethylene vinyl acetate copolymer replaces water, obtains gel.The hardness of measuring gel after 3 hours is 300g/cm 2Embodiment 6
The 70wt% aqueous solution, the 73.7g (0.55mol) 3 that in a 500mL four neck flasks, pack into and contain 120g (0.55mol) D-Xylitol, 4-dimethylbenzaldehyde and 12g 50wt% sulfuric acid.Go out air in the reaction system with nitrogen replacement.Material in 21 ℃ of stirred flask 6 hours.Analyze the gained reaction mixture with GC, find that the productive rate of single (3, the 4-dimethyl benzylidene)-D-Xylitol is 70%, productive rate≤0.5% of two (3, the 4-dimethyl benzylidene)-D-Xylitols.Place and use 8.6g potassium hydroxide neutralization reaction mixture 2 hours after 24 hours, filter and obtain filter cake.Be dispersed in filter cake in the 150mL toluene and filtration once more.Obtain 44.5g 2 to the 5mmHg pressure range after dry 7 hours at 100 ℃ of normal pressures, 4-O-(3, the 4-dimethyl benzylidene)-D-Xylitol, GC measuring result purity is 99.2% (productive rate 30.1%).The fusing point of product is 179.5-180.0 ℃.
Repeat with embodiment 1 same step, just with top gained 2,4-O-(3, the 4-dimethyl benzylidene)-D-Xylitol replaces 2, and 4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder obtains gel.The hardness of measuring gel after 3 hours is 250g/cm 2Embodiment 7
Repeat with embodiment 2 same steps, just with 2,4-O-(3, the 4-dimethyl benzylidene)-D-Xylitol replaces 2, and 4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder obtains gel.The hardness of measuring gel after 3 hours is 240g/cm 2Embodiment 8
The 70wt% aqueous solution, the 35.0g (0.20mol) 3 that in a 500mL four neck flasks, pack into and contain 52g (0.20mol) D-Sorbitol Powder, 4-dichlorobenzaldehyde and 6g 50wt% sulfuric acid.Go out air in the reaction system with nitrogen replacement.Material in 21 ℃ of stirred flask 6 hours.Analyze the gained reaction mixture with GC, find that the productive rate of single (3, the 4-dichlorin benzylidene)-D-Sorbitol Powder is 70%, productive rate≤0.5% of two (3, the 4-dichlorin benzylidene)-D-sorbyl alcohols.Place and use 8.6g potassium hydroxide neutralization reaction mixture 2 hours after 24 hours, filter and obtain filter cake.Be dispersed in filter cake in the 150mL toluene and filtration once more.Obtain 19.7g 2 to the 5mmHg pressure range after dry 7 hours at 100 ℃ of normal pressures, 4-O-(3, the 4-dichlorin benzylidene)-D-sorbyl alcohol, GC measuring result purity is 99.2% (productive rate 29.2%).The fusing point of product is 202-205 ℃.
Repeat with embodiment 2 same steps, just with top gained 2,4-O-(3, the 4-dichlorin benzylidene)-D-Sorbitol Powder replaces 2, and 4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder obtains gel.The hardness of measuring gel after 3 hours is 250g/cm 2Embodiment 9
In the 300mL beaker, pack into 99.5g water and 0.5g embodiment 1 gained 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder.Material in the beaker is heated to 90 ℃, stirs simultaneously.Obtain the solution of homogeneous transparent after 1 minute.This solution (20mL) is poured in the 300mL sample beaker, and quenching in 20 ℃ of water-baths obtained clear gel after 8 hours.The hardness of measuring gel after 24 hours is 100g/cm 2Gel is heated to 90 ℃ once more, and the gel heating reversibly changes back to homogeneous solution.In the same way as described above with this solution quenching, obtain identical gel after 8 hours once more.Embodiment 10
In 300mL four neck flasks, add 65g water, 20g glycerine, 5g glycol salicylate, 5g wintergreen oil and 5gL-methyl alcohol.Material in the flask in stirring at room, is obtained homogeneous solution.Add the gelling agent powder [2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder] that 1.5g embodiment 1 obtains therein.With mixture heating up to 90 ℃, stir simultaneously, obtain solution.After being cooled to 80 ℃ solution is poured in the stainless steel vat, allowed solution in bucket, continue cool to room temperature.Form the thick gel of 2mm after 2 minutes.Cut off a 5 * 5cm 2Gel, it is covered on the scratch mark of arm, then, the injury wraps with bandage.Tangible anti-inflammatory and analgesic effect are arranged after 2 minutes certainly.Embodiment 11
The gelling agent powder [2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder] that 0.8g embodiment 1 is obtained is added in the aqueous solution of polyvinyl alcohol (Mn=10,100) of 100g 8wt%.With mixture heating up to 90 ℃, stir simultaneously, obtain colloidal sol.After being cooled to 40 ℃ colloidal sol is covered on the human body skin.The colloidal sol covering becomes the gel covering after 5 minutes.If peel the gel covering off, the dust spot of covering on skin will be removed.Comparing embodiment 1
With embodiment 11 same quadrat methods, just without jelling agent, preparation colloidal sol.Colloidal sol is covered on the human body skin, need 30 minutes but form film.
Performance in following embodiment and the reference example is measured with following method.Measure gel hardness
The gel that at first prepares predetermined amount.At diameter 4cm, measure gel 1 day or the gel hardness after 1 month with the instrument (Kiya Seisakusho Ltd. manufacturing) of measuring the agar setting strength in the beaker of high 6cm.Except as otherwise noted, the sugar compounds concentration in the gelatinous composition is 1wt% in the following example.Therefore, the gel hardness that obtains is used as gain.It is high more to gain, and gel is stable more.The HLB value
The HLB value of poly suboxygen alkyl alkyl oxide is to calculate with Griffin equation (W.C.Griffin, " chemist, makeup association magazine (J.Soc.Cosmetic, Chemists) ", 1,1180 (1949)).The HLB value of the nonionogenic tenside outside the Voranol EP 2001 is shown in the products catalogue.The Griffin equation
HLB=20 * (molecular weight of the molecular weight/tensio-active agent of the hydrophilic radical in the tensio-active agent)
If gel still keeps its original shape after 1 month, illustrate that then it is stable.Embodiment 12
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder, 200mg CONION 275 (90) (trade(brand)names, New Japan ChemicalCo., Ltd. product, mainly contain the alcohol of 12 carbon atoms and average mol and be the product of 9 oxyethane addition reaction, HLB=13.5) and 10mg K 2CO 3Be added in the 100mL water.Make three kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/0.2) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition.After 1 day, the hardness of gelatinous composition is 600g/cm 2Embodiment 13
The gelatinous composition that embodiment 12 is obtained in dry ice-propanone is bathed in-78 ℃ freezing 2 hours, (pressure drops to 10 with the vacuum pump decompression with composition then -4MmHg) dry (this process is called as " freeze-drying ") 24 hours, obtaining the 1.2g latex agent composition is white powder.Embodiment 14
10mL water is added in the latex agent composition (calculating concentration of sugar compounds is 1wt%) that 140mg embodiment 13 obtains, and water is gelling at once.The hardness of gained gelatinous composition is 350g/cm after 1 day 2After 1 month, it is stable that gel keeps, and its hardness is 380g/cm 2Embodiment 15
10mL water is added in the latex agent composition (calculating concentration of sugar compounds is 3wt%) that 400mg embodiment 13 obtains, and water is gelling at once.The hardness of gained gelatinous composition is 380g/cm after 1 day 2After 1 month, it is stable that gel keeps, and its hardness is 400g/cm 2Embodiment 16
The artificial urine of 10mL is added in the latex agent composition (calculating concentration of sugar compounds is 1wt%) that 140mg embodiment 13 obtains artificial urine gelling after about 30 minutes.The hardness of gained gelatinous composition is 260g/cm after 1 day 2(composition of artificial urine: 1.94wt% urea, 0.8wt% sodium-chlor, 0.06wt% calcium chloride, 0.11wt% sal epsom and 97.09wt% water).Embodiment 17
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder, 1.0g CONION 275 (60) (trade(brand)names, New Japan Chemical Co., Ltd. product, mainly contain the alcohol of 12 carbon atoms and average mol and be the product of 6 oxyethane addition reaction, HLB=11.5) and 10mg K 2CO 3Be added in the 100mL water.Make three kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/1) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition.After 1 day, the hardness of gelatinous composition is 550g/cm 2This gelatinous composition is freezing in-78 ℃ of dry ice-propanones are bathed, then with vacuum pump with composition freeze-drying 24 hours, obtaining the 2.0g latex agent composition is white powder.Embodiment 18
1.0g sand and 10mL water are added in the latex agent composition that 120mg embodiment 17 obtains, and water is gelling at once.The hardness of gained gelatinous composition is 350g/cm after 1 day 2The same gelling that is shaped in the upright pipe of placing (being made internal diameter 35mm, length 100mm by acryl) splash into gel from the top Jiang Shui of pipe, but water can not penetrate gel, with this water holding effect of gel is described.Embodiment 19
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder, 2.0g CONION 275 (60) and 10mg K 2CO 3Be added in the 100mL water.Make three kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/2) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition.After 1 day, the hardness of gelatinous composition is 600g/cm 2This gelatinous composition is freezing in-78 ℃ of dry ice-propanones are bathed, then with vacuum pump with composition freeze-drying 24 hours, obtaining the 2.98g latex agent composition is white powder.Embodiment 20
10mL water is added in the latex agent composition that 300mg embodiment 19 obtains, and water is gelling at once.The hardness of gained gelatinous composition is 300g/cm after 1 day 2After 1 month, it is stable that gel keeps, and its hardness is 350g/cm 2Embodiment 21
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder, 600mg Sodium dodecylbenzene sulfonate (Nacalai Tesque Co., the product of Ltd.) and 10mg K 2CO 3Be added in the 100mL water.Make three kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/0.6) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition.After 1 day, the hardness of gelatinous composition is 450g/cm 2This gelatinous composition is freezing in-78 ℃ of dry ice-propanones are bathed, then with vacuum pump with composition freeze-drying 24 hours, obtaining the 1.6g latex agent composition is white powder.Embodiment 22
10mL water is added in the latex agent composition that 120mg embodiment 21 obtains, and water is gelling at once.The hardness of gained gelatinous composition is 320g/cm after 1 day 2After 1 month, it is stable that gel keeps, and its hardness is 320g/cm 2Embodiment 23
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder, 3.0g N-NON A2020A5S (trade(brand)name, New Japan Chemical Co., Ltd. product, polyoxyethylene (participating in reaction for 20 moles)-2-hydroxyl lauryl ether is HLB=15.2) with 10mg K 2CO 3Be added in the 100mL water.Make three kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/3) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition.After 1 day, the hardness of gelatinous composition is 600g/cm 2This gelatinous composition is freezing in-78 ℃ of dry ice-propanones are bathed, then with vacuum pump with composition freeze-drying 24 hours, obtaining the 4.0g latex agent composition is white powder.Embodiment 24
10mL water is added in the latex agent composition that 120mg embodiment 23 obtains, and water is gelling at once.The hardness of gained gelatinous composition is 280g/cm after 1 day 2After 1 month, it is stable that gel keeps, and its hardness is 300g/cm 2Embodiment 25
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder, 200mg Riponox100 (trade(brand)name, Lion Co., the product of Ltd., polyoxyethylene nonylphenol, HLB (being shown in products catalogue)=13.3) and 10mg K 2CO 3Be added in the 100mL water.Make three kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/0.2) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition.This gelatinous composition is freezing in-78 ℃ of dry ice-propanones are bathed, then with vacuum pump with composition freeze-drying 24 hours, obtaining the 1.2g latex agent composition is white powder.Embodiment 26
10mL water is added in the latex agent composition that 120mg embodiment 25 obtains, and water is gelling at once.The hardness of gained gelatinous composition is 320g/cm after 1 day 2After 1 month, it is stable that gel keeps, and its hardness is 330g/cm 2Embodiment 27
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder, 700mg APG-600 (trade(brand)name, Henkel Hakusui Co., Ltd. product, alkyl chain length is the chain length that mainly contains the alkyl dextran glycosides of 12 carbon atoms, and mean polymerisation degree is 1.4, HLB (being shown in products catalogue)=13.5) and 10mg K 2CO 3Be added in the 100mL water.Make three kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/0.7) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition.This gelatinous composition is freezing in-78 ℃ of dry ice-propanones are bathed, then with vacuum pump with composition freeze-drying 24 hours, obtaining the 1.7g latex agent composition is white powder.Embodiment 28
10mL water is added in the latex agent composition that 120mg embodiment 27 obtains, and water is gelling at once.The hardness of gained gelatinous composition is 320g/cm after 1 day 2After 1 month, it is stable that gel keeps, and its hardness is 350g/cm 2Embodiment 29
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder, 200mg monolaurin (monolaurin, Nacalai Tesque Co., the product of Ltd.) and 10mg K 2CO 3Be added in the 100mL water.Make three kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/0.2) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition.This gelatinous composition is freezing in-78 ℃ of dry ice-propanones are bathed, then with vacuum pump with composition freeze-drying 24 hours, obtaining the 1.2g latex agent composition is white powder.Embodiment 30
10mL water is added in the latex agent composition that 120mg embodiment 29 obtains, and water is gelling at once.The hardness of gained gelatinous composition is 220g/cm after 1 day 2After 1 month, it is stable that gel keeps, and its hardness is 200g/cm 2Embodiment 31
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder, 200mg AmizolCDE (trade(brand)name, Kawaken Fine Chemical Co., the product of Ltd., cocoanut fatty acid diethanolamide) and 10mg K 2CO 3Be added in the 100mL water.Make three kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/0.2) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition.This gelatinous composition is freezing in-78 ℃ of dry ice-propanones are bathed, then with vacuum pump with composition freeze-drying 24 hours, obtaining the 1.2g latex agent composition is white powder.Embodiment 32
10mL water is added in the latex agent composition that 120mg embodiment 31 obtains, and water is gelling at once.The hardness of gained gelatinous composition is 300g/cm after 1 day 2After 1 month, it is stable that gel keeps, and its hardness is 300g/cm 2Embodiment 33
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder and 500mg sodium oleate (Nacalai Tesque Co., the product of Ltd.) are added in the 100mL water.Make two kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/0.5) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition.This gelatinous composition is freezing in-78 ℃ of dry ice-propanones are bathed, then with vacuum pump with composition freeze-drying 24 hours, obtaining the 1.5g latex agent composition is white powder.Embodiment 34
10mL water is added in the latex agent composition that 150mg embodiment 33 obtains, and glue coagulates after about 60 minutes.The hardness of gained gelatinous composition is 170g/cm after 1 day 2Embodiment 35
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder and 200mg Arcard T-800 (trade(brand)name, LionCo., the product of Ltd., stearyl-trimethyl ammonium chloride) are added in the 100mL water.Make two kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/0.2) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition.Gelatinous composition is freezing in-78 ℃ of dry ice-propanones are bathed, use vacuum pump freeze-drying said composition 24 hours then, obtaining the 1.2g latex agent composition is white powder.Embodiment 36
10mL water is added in the latex agent composition that 200mg obtains by embodiment 35, and glue needs 60 minutes with fixed attention approximately.The hardness of gained gelatinous composition is 100g/cm after 1 day 2Embodiment 37
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder and 200mg RIKABIONA 100 (trade(brand)name, New Japan Chemical Co., the product of Ltd., lauryl dimethyl Padil trimethyl-glycine) are added in the 100mL water.Make two kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/0.2) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition.Gelatinous composition is freezing in-78 ℃ of dry ice-propanones are bathed, use vacuum pump freeze-drying said composition 24 hours then, obtaining the 1.2g latex agent composition is white powder.Embodiment 38
10mL water is added in the latex agent composition that 150mg obtains by embodiment 37, and glue needs 60 minutes with fixed attention approximately.The hardness of gained gelatinous composition is 100g/cm after 1 day 2Embodiment 39
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder, 4.0g glycerine (NacalaiTesque Co., the product of Ltd.) and 10mg K 2CO 3Be added in the 100mL water.Make three kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/4) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition, hardness is 240g/cm 2Gelatinous composition is freezing in-78 ℃ of dry ice-propanones are bathed, use vacuum pump freeze-drying said composition 24 hours then, obtaining the 5.0g latex agent composition is white powder.Embodiment 40
10mL water is added in the latex agent composition that 500mg obtains by embodiment 39, and glue needs 120 minutes with fixed attention approximately.The hardness of gained gelatinous composition is 80g/cm after 1 day 2Embodiment 41
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder, 200mg polyoxyethylene glycol #6000 (trade(brand)name, Nacalai Tesque Co., the product of Ltd.) and 10mg K 2CO 3Be added in the 100mL water.Make three kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/0.2) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition, hardness is 280g/cm 2In dry this gelatinous composition of 90 ℃ of decompressions (2mmHg), obtaining the 1.2g latex agent composition is white powder.Embodiment 42
10mL water is added in the latex agent composition that 120mg obtains by embodiment 41, and glue needs 360 minutes with fixed attention approximately.The hardness of gained gelatinous composition is 210g/cm after 1 day 2Gel keeps stable after 1 month, and hardness is 200g/cm 2Embodiment 43
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-the D-Sorbitol Powder pounds into powder, then with itself and 2.0g CONION 2P (50) (trade(brand)name, New Japan Chemical Co., Ltd. product mainly contains the alcohol of 12 carbon atoms and average mol and is the product of the addition reaction of 5 oxyethane, HLB=12.8) and 10mg K 2CO 3Mix.This mixture fully with after 4.0mL water mixes is shut the reactor opening.Allow mixture obtain pie latex agent composition (weight ratio: sugar compounds/dispersion agent=1/2) through 7 days after aging at 50 ℃.Embodiment 44
10mL water is added in the latex agent composition that 1.0g obtains by embodiment 43, and glue needs 60 minutes with fixed attention approximately.The hardness of gained gelatinous composition is 100g/cm after 1 day 2Reference example 1
10mL water is added to 100mg 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder and lmgK 2CO 3Mixture in.With this mixture in stirring at room.Mixture does not still form gel for the suspension state after 24 hours.And when being heated 98 ℃, suspension has become colloidal sol.Colloidal sol is quenched to 25 ℃, obtains gel.The hardness of gel is 280g/cm after 1 day 2Reference example 2
The gel that reference example 1 is obtained is cooled to-78 ℃, freezing gel.With vacuum pump lyophilised gel 24 hours, remove and anhydrate, obtain powder crystal shape jelling agent (dry gel powder).The jelling agent that obtains like this is suspended in 10mL water, makes powder be combined into piece.The outer rim of caking becomes flexible glue (sol-gel material) after 48 hours, therefore can't measure its hardness (less than 60g/cm 2).Embodiment 45
With 1.0g Wandamine OX-300 (trade(brand)name, New Japan Chemical Co., the product of Ltd., lauryl dimethylamine oxide) and 10mg K 2CO 3Be added in the jelling agent of the dry gel powder powder that 1.0g obtains by reference example 2.Obtain 2.0g pie latex agent composition (weight ratio: sugar compounds/dispersion agent=1/1) after the stirring.Embodiment 46
5.0mL water is added in the latex agent composition that 1.0g obtains by embodiment 45, and glue needs 120 minutes with fixed attention approximately.The hardness of gained gelatinous composition is 80g/cm after 1 day 2Reference example 3
With 300mg 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder and 10mg K 2CO 3Be added in the 10mL water (concentration of sugar compounds is 3wt%).Make two kinds of compositions be dissolved in water 98 ℃ of heating.Solution is cooled to 25 ℃, and the result is settled out crystal, does not form gel.Reference example 4
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder, 4mg CONION 275 (90) and 10mg K 2CO 3Be added in the 100mL water.Make three kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/0.004) 98 ℃ of heating.Solution is cooled to 25 ℃, obtains gelatinous composition.With gelatinous composition in-78 ℃ of dry ice-propanones are bathed freezing 2 hours, use vacuum pump freeze-drying said composition 24 hours then, obtaining the 1000mg latex agent composition is white powder.10mL water is added in the 100mg gained latex agent composition, and powder is combined into piece as a result.The outer rim of caking becomes flexible glue (sol-gel material) after 48 hours, therefore can't measure its hardness (less than 60g/cm 2).Reference example 5
With 1.0g 2,4-O-(3, the 4-dimethyl benzylidene)-D-Sorbitol Powder, 11g CONION 275 (90) and 10mg K 2CO 3Be added in the 100mL water.Make three kinds of compositions be dissolved in water (weight ratio: sugar compounds/dispersion agent=1/11) 98 ℃ of heating.Solution is cooled to 25 ℃, but does not form gel.

Claims (20)

  1. Formula (1) or formula (2) representative sugar compounds,
    Figure A9718003900021
    Figure A9718003900022
    Wherein, R 1And R 2Identical or different, representative has the alkyl of 1-3 carbon atom, the alkoxyl group that 1-3 carbon atom arranged or halogen atom separately, and p is 0 or 1.
  2. 2. according to the sugar compounds of claim 1, each R wherein 1And R 2Equal represent methylidene.
  3. 3. formula, (1) or likes, the preparation method of sugar compounds (2), this method may further comprise the steps: with sugar alcohol, (A) and benzaldehyde derivative, (B) dehydrating condensation in water or organic solvent, sugar alcohol wherein, (A) be selected from least a in Sorbitol Powder and the Xylitol, and described benzaldehyde derivative, (B) be to be selected from formula, (3) 3 of expression, dibasic phenyl aldehyde of 4-and formula, (4) 3 of expression, at least a in the dialkyl ether of the dibasic phenyl aldehyde of 4-, sugar alcohol, (A) and benzaldehyde derivative, (B) mol ratio, (A/B) be 2/1 to 1/2
    Figure A9718003900031
    Figure A9718003900032
    Figure A9718003900034
    Wherein, R 1And R 2Identical or different, representative has the alkyl of 1-3 carbon atom, the alkoxyl group that 1-3 carbon atom arranged or halogen atom, R separately 3Representative has the alkyl of 1-4 carbon atom, and p is 0 or 1.
  4. 4. according to the method for claim 3, wherein dehydration condensation carries out not being higher than under 80 ℃ the temperature of reaction in the presence of an acidic catalyst.
  5. 5. the organic gelling agent that contains at least a sugar compounds as claim 1 definition.
  6. 6. contain water medium and as the gel of the organic gelling agent of claim 5 definition.
  7. 7. according to the gel of claim 6, wherein water medium is water, the aqueous solution, water miscible liquid or aqueous dispersions.
  8. 8. according to the gel of claim 6, wherein water medium is the aqueous solution, water miscible liquid or the aqueous dispersions that contains water-soluble polymers and/or inorganic salt.
  9. 9. according to the gel of claim 6, wherein water medium is the water miscible liquid that contains ethylene vinyl acetate copolymer.
  10. 10. the method for preparing gel comprises by heating making the organic gelling agent of claim 5 be dissolved in water medium to obtain a kind of solution, then with described solution refrigerative step.
  11. 11. be used for the gel of medical purpose, wherein the gel of claim 6 contains the medicine of percutaneous dosing.
  12. 12. be used for the gel of makeup purpose, wherein the gel of claim 6 contains the activeconstituents of make-up composition.
  13. 13. latex agent composition, contain at least a sugar compounds in the sugar compounds of the sugar compounds of the formula that is selected from (1) expression of 100 weight parts and formula (2) expression and at least a dispersion agent that is selected from following material of 1-1000 weight part: nonionogenic tenside, anion surfactant, cats product, amphoterics and hydrophilic organic solvent;
    Figure A9718003900041
    Figure A9718003900051
    Wherein, R 1And R 2Identical or different, representative has the alkyl of 1-3 carbon atom, the alkoxyl group that 1-3 carbon atom arranged or halogen atom separately, and p is 0 or 1.
  14. 14. according to the latex agent composition of claim 13, wherein this latex agent composition just contains the dispersion agent of 10-500 weight part with respect to the sugar compounds that whenever contains 100 weight parts.
  15. 15. according to the latex agent composition of claim 13, wherein said sugar compounds is the dry gel powder form.
  16. 16. according to the latex agent composition of claim 13, wherein dispersion agent is a nonionogenic tenside.
  17. 17. according to the latex agent composition of claim 13, the R in its Chinese style (1) or the formula (2) 1And R 2All are methyl.
  18. 18. the preparation method of latex agent composition, this method may further comprise the steps: at least a sugar compounds, dispersion agent and the medium in the sugar compounds prepares gel shown in sugar compounds shown in the formula (1) and the formula (2) with being selected from, from gel, described medium is removed then Wherein, R 1And R 2Identical or different, representative has the alkyl of 1-3 carbon atom, the alkoxyl group that 1-3 carbon atom arranged or halogen atom separately, and p is 0 or 1.
  19. 19. according to the method for claim 18, wherein that gel is freezing, and pressure reduced to below the vapour pressure that is frozen medium from the refrigerated gel, remove medium.
  20. 20. a gelatinous composition comprises the described latex agent composition of water medium and claim 13.
CN97180039A 1996-11-28 1997-11-21 Sugar compounds, gelling agents, gelling agent compositions, processes for the preparation of them and gel compositions Expired - Fee Related CN1101389C (en)

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